Isocyanate-derived materials for use in phase change ink jet inks

ABSTRACT

Resins and waxes made by reacting selected nucleophiles, including alcohols and/or amines, with an isocyanate are disclosed. The order of addition of the isocyanate and the different nucleophiles can tailor the distribution of di-urethane, mixed urethane/urea, and/or di-urea molecules in the final resin product. The isocyanate-derived resin and wax materials are useful as ingredients as phase change ink carrier compositions used to make phase change ink jet inks.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to resins or waxes made by reactingisocyanates with selected nucleophiles such as alcohols and/or amines.The nucleophiles can be used singly or in combinations to achievecertain desirable properties in the resins. The present invention alsorelates to phase change ink compositions, both generally and in specificcompositions, containing such resins and/or waxes. More particularly,the present invention employs the use of an isocyanate-derivedurethane/urea resin, which is the condensation reaction product of atleast one alcohol precursor, an isocyanate precursor and at least oneamine precursor. The present invention also covers a phase change inkcarrier composition and the ink formed from the isocyanate-derivedresin, a tackifier resin, a mono-amide and a colorant. Still further,the present invention relates to the process of using such phase changeink compositions containing such resins and/or waxes in a printingdevice.

2. Description of the Relevant Art

In general, phase change inks (sometimes referred to as "hot melt inks")are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the printing media, they quickly solidify to form apredetermined pattern of solidified ink drops. Phase change inks havealso been investigated for use in other printing technologies such asgravure printing as referenced in U.S. Pat. No. 5,496,879 and Germanpatent publications DE 4205636AL and DE 4205713AL assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co.

Phase change inks for color printing generally comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. Preferably, a colored phase change ink will beformed by combining the above-described ink carrier composition withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks of this invention can comprise four componentdyes, namely, cyan, magenta, yellow and black. U.S. Pat. Nos. 4,889,506;4,889,761; and 5,372,852 teach that the subtractive primary colorantsemployed typically may comprise dyes from the classes of Color Index(C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and alimited number of Basic Dyes. The colorants can also include pigments asexemplified in U.S. Pat. No. 5,221,335, assigned to CoatesElectrographics LTD. U.S. patent application Ser. No. 08/381,610, nowU.S. Pat. No. 5,621,022 filed Jan. 30, 1995, and assigned to Tektronix,Inc., is directed to the use of a specific class of polymeric dyes inphase change ink compositions.

Phase change inks are desirable for ink jet printers since they remainin a solid phase at room temperature during shipping, long-term storage,and the like. Also, the problems associated with nozzle clogging due toink evaporation are largely eliminated, thereby improving thereliability of ink jet printing. Furthermore, in the above-noted priorart phase change ink jet printers where the ink droplets are applieddirectly onto the printing medium the droplets solidify immediately uponcontact with the substrate, migration of ink along the printing mediumis prevented and dot quality is improved. This is also true of theprocesses and ink compositions described herein.

In addition to the above-referenced U.S. patents, many other patentsdescribe materials for use in phase change ink jet inks. Somerepresentative examples include U.S. Pat. Nos. 3,653,932; 4,390,369;4,484,948; 4,684,956; 4,851,045; 4,889,560; 5,006,170; and 5,151,120; aswell as EP Application Nos. 0187352 and 0206286. These materials caninclude paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide-containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters are an example) andmany synthetic resins, oligomers, polymers and co-polymers.

Separately, PCT Patent Application WO 94/14902, which was published onJul. 7, 1994 and is assigned to Coates Brothers PLC, teaches a hot meltink containing a colorant and, as a vehicle for the hot melt ink, anoligourethane having a melting point of at least 65° C. and obtained byreacting an aliphatic or aromatic diisocyanate with at least astoichiometric amount of either: (i) a monohydric alcohol component; or(ii) a monohydric alcohol component followed by another differentmonohydric alcohol component; or (iii) a monohydric alcohol component,followed by a dihydric alcohol component, followed by a monohydricalcohol component.

This PCT patent application defines the monohydric alcohol component aseither a monohydric aliphatic alcohol (e.g. C₁ to C₂₂ alcohols), anetherified dihydric aliphatic alcohol (e.g. propylene glycol methylether (PGME), dipropylene glycol methyl ether (DPGME), ethylene glycolbutyl ether (EGBE), diethylene glycol butyl ether (DPGBE), tripropyleneglycol butyl ether (TPGBE) and propylene glycol phenyl ether (PPL));esterified dihydric aliphatic alcohol (e.g. the esterifying acid may bean ethylenically unsaturated acid (such as acrylic acid or methacrylicacid), thereby introducing ethylenic unsaturation into the oligourethaneand rendering it suitable for eventual further additional polymerization(curing) after having been applied to a substrate by hot melt printing),or dihydric polyalkylene glycol. This PCT Application further definedthe dihydric alcohol component as a dihydric aliphatic alcohol or adihydric polyalkylene glycol (e.g. ethylene glycol, polyethylene glycol(PEG 1500), polypropylene glycol (PPG 750, 1000 and 1500), trimethyleneglycol, dipropylene glycol, methylpropanediol and 1,6-hexanediol).

Also, PCT Patent Application WO 94/04619, assigned to the GeneralElectric Company, teaches the use of ionomeric materials in combinationwith image forming agents to form a hot melt ink jet ink. The ionomericmaterials can include many different types of copolymeric or polymericionomers, including carboxyl-functional polyurethanes prepared from adiol or polyol and a hydroxyl acid. Many other carrier materials andcolorants for the image forming agent of the invention are included inthis PCT application.

There is still a need for new materials for novel and differentapplications of phase change inks. There is also a need for relativelylow viscosity resins, including non-polymeric resins, and waxes designedfor phase change ink jet and other forms of phase change ink printing.These needs are solved by the present invention by providing a means totailor the properties of these resin and wax isocyanate-derivedmaterials for specific applications.

BRIEF SUMMARY OF THE INVENTION

It is an aspect of the present invention that urethane compoundscomprising the reaction product of selected isocyanates with selectedalcohols or mixtures of selected alcohols are obtained.

It is another aspect of the present invention that urea compoundscomprising the reaction product of selected isocyanates with selectedamines or mixtures of selected amines are obtained.

It is still another aspect of the present invention that urethane/ureacompounds comprising the reaction product of selected isocyanates withmixtures of selected alcohols and amines are obtained.

It is still a further aspect of the present invention that a phasechange ink composition comprising an admixture of (a) a phase changecarrier composition containing at least one isocyanate-derived resin orwax, and (b) a phase change ink compatible colorant is obtained.

It is yet another aspect of the present invention that a method forproducing a layer of a phase change colored ink on the surface of asubstrate by either direct or indirect printing is obtained wherein thephase change ink composition in the solid phase comprises an admixtureof (a) a phase change carrier composition containing at least oneisocyanate-derived resin or wax and (b) a phase change ink compatiblecolorant.

It is a feature of the present invention that the colorless isocyanatederived resin or wax reaction product of the selected isocyanates withselected alcohols or mixtures of selected alcohols and/or selectedamines or mixtures of selected amines obviates the need for the use of aseparate plasticizer when the resin is employed in an ink formulationbecause the resulting ink is sufficiently malleable and ductile on itsown.

It is an advantage of the present invention that the isocyanate-derivedresins or waxes can be design engineered to obtain desired propertiesfor specific printing platforms and architectures.

It is another advantage of the present invention that theisocyanate-derived resins or waxes are very pure, being free of saltsand other insoluble contaminants.

It is still another advantage of the present invention that theisocyanate-derived resins can be used in combinations with other phasechange ink carrier materials to obtain ink compositions that displayimproved yield stress versus temperature curves over prior art inkcompositions.

It is yet another advantage of the present invention that theisocyanate-derived resins are transparent.

It is yet further advantage of the present invention that theisocyanate-derived resins may be substituted for one or more componentsin prior fatty amide containing phase change inks, such as thetetra-amide, mono-amide, tackifier, or plasticizer components.

These and other aspects, features and advantages are obtained by the useof reaction products of selected isocyanates with selected alcoholsand/or amines to produce isocyanate-derived resins or waxes suitable foruse in phase change inks that may be employed in direct or indirectprinting applications.

BRIEF DESCRIPTION OF THE DRAWINGS

The aspects, features, and advantages of the invention will becomeapparent upon consideration of the following detailed disclosure of theinvention; especially when it is taken in conjunction of theaccompanying drawing wherein:

FIG. 1 is a graphical illustration of the yield stress versustemperature curve of ink from Example 20 compared to a prior art phasechange ink, wherein the test ink from Example 20 is represented by smallsquares and the prior art ink is shown by small diamonds.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "nucleophile" in the present specification and claims is usedas defined on page 179 of "Advanced Organic Chemistry", 3rd Edition byJerry March, ©1985 by John Wiley and Sons, to describe a reagent thatbrings an electron pair to a reaction to form a new bond. The preferrednucleophiles of this invention are alcohols or amines, but it isunderstood that other nucleophilic functional groups that are capable ofreacting with the isocyanate moiety could also be used in the invention.

The term "oligomer" in the current specification and claims is used asdefined on page 7 of "Polymer Chemistry--The Basic Concepts" by PaulHiemenz, ©1984 by Marcel Dekker, Inc., to describe a term coined todesignate molecules for which n (representing the number of repeatingmonomer units) is less than 10.

The term "isocyanate-derived resin or material" as used in the presentspecification and claims is defined as any monomeric, oligomeric ornon-polymeric resinous material derived from the reaction of mono-, di-,or poly-isocyanates with suitable nucleophilic molecules.

The term "isocyanate-derived wax" as used in the present specificationand claims is defined as any crystalline or semicrystalline waxymaterial derived from the reaction of a fatty isocyanate with a suitablenucleophile, or the reaction of a fatty nucleophile with a suitableisocyanate, or the reaction of a fatty nucleophile with a fattyisocyanate.

Any suitable reaction condition for making urethane or urea compounds bycondensing alcohols and/or amines with isocyanates may be employed inthe practice of the present invention. Preferably, the reaction iscarried out at elevated temperatures (e.g. about 60° C. to about 160°C.) in the presence of a urethane reaction catalyst such asdibutyltindilaurate, bismuth tris-neodecanoate, cobalt benzoate, lithiumacetate, stannous octoate or triethylamine. The reaction conditionspreferably are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable atmosphere, to prevent oxidizing oryellowing the reaction products and to prevent undesirable sidereactions. The mole ratio of reactants is adjusted so that theisocyanate functionalities are completely consumed in the reaction witha slight molar excess of alcohol or amine typically remaining.Conceptually the reactants can be added together in any order and/oradded to the reaction as physical mixtures. However, in the preferredembodiments of the invention, reaction conditions and the order of theaddition of reactants are carefully controlled for several reasons.First, reaction conditions and reactant additions are chosen to providea controlled exothermic reaction. Secondly, when reacting mixtures ofalcohols and/or amines with diisocyanates such as isophoronediisocyanate (IPDI), the order of addition of the isocyanate and thedifferent nucleophiles to the reaction is chosen to tailor thedistribution of diurethane molecules, and/or mixed urethane/ureamolecules, and/or diurea molecules in the final resin or material. Whendoing this, the different reactivities to isocyanates of alcohols versusamines are employed, as are the different reactivities of the twoseparate isocyanate groups on IPDI. See J. H. Saunders and K. C.Frisch's "Polyurethanes Part I, Chemistry" published by Interscience ofNew York, N.Y. in 1962 and Olin Chemicals' Luxate® IM isophoronediisocyanate technical product information sheet which provide furtherexplanation of this chemistry. This control of the reaction conditionsand order of addition of the reactants is done to specifically tailor orcustomize the different types of molecular species in the finished resinso that the resin will:

(1) have a controlled viscosity that is designed for a specificapplication,

(2) have a controlled glass transition temperature and/or melting point,and

(3) have consistent properties from batch to batch.

The isocyanate-derived resins or materials from these reactions aregenerally transparent solids having melting points in the range of about20° C. to about 150° C., viscosities in the range of about 10 cPs toabout 5000 cPs at 150° C. and T_(g) 's of about -30° C. to about 100° C.The isocyanate-derived waxes from these reactions are generally opaquewaxy solids having sharp melting points from about 50° C. to about 130°C., and viscosities of about 1 cPs to about 25 cPs at 140° C. Theisocyanate-derived resins or materials and waxes display properties suchthat the higher the T_(g) and the melting point, the higher is theviscosity. While the structural activity relationships are not fullyunderstood, it is known that the T_(g) of the isocyanate-derived resinsor materials is controlled by the proper choice of the mixture ofnucleophiles in the reaction as illustrated in Table 3 below. Varyingone or more of the readily available commodity chemicals used aschemical precursors will permit custom-tailoring of the properties ofthe isocyanate-derived resin and wax materials.

Preferred alcohols to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins or materials of thisinvention include any monohydric alcohol. For instance, the monohydricalcohol could be any aliphatic alcohol e.g., a C₁ -C₂₂ or higher linearalcohol, any branched alcohol or any cyclic aliphatic alcohol such asmethanol, ethanol, (n- and iso)-propanol, (n-, iso-, t-) butanol, (n-,iso-, t-, and the like) pentanol, (n-, iso-, t-, and the like) hexanol,(n-, iso-, t-, and the like) octanol, (n-, iso-, t-, and the like)nonanol, (n- and branched) decanols, (n- and branched) undecanols, (n-and branched) dodecanols, (n- and branched) hexadecanols, (n- andbranched) octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like!; analiphatic/aromatic alcohol e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates of octyl, nonyl, and dodecylphenol, andalkoxyphenol!; aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like) and othersuitable alcohols (e.g., N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like). It will be obvious to those skilled in theart that small amounts (on a molar basis) of polyols could also beincorporated into the reaction mixture to produce oligomeric species inthe resins if so desired. The preferred alcohols are hydroabietylalcohol, octylphenol ethoxylate and octadecyl alcohol.

Preferred amines to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins or materials of thisinvention include any monofunctional amine, with the exception oftertiary amines void of other nucleophilic functional groups (e.g.,triethylamine). For instance, the monoamine could be any aliphaticprimary or secondary amine (e.g., a C₁ -C₂₂ or higher linear amine, anybranched amine or any cyclic aliphatic amine) such as methyl amine,ethyl amine, (n- and iso-)propyl amine, (n-, iso-, and t-) butyl amine,(n-, iso-, t-, and the like) pentyl amine, (n-, iso-, t-, and the like)hexyl amine, (n-, iso-,t-, and the like) octyl amine, (n-, iso-, t-, andthe like) nonyl amine, (n- and branched) decyl amine, (n- and branched)undecyl amines, (n- and branched) dodecyl amines, (n- and branched)hexadecyl amines, (n- and branched) dodecyl amines, dimethyl amine,diethyl amine, di(n- and iso-)propyl amines, di(n-, iso-, t-)butylamine, di(n-, iso-, t-, and the like)pentyl amine, di(n-, iso-, t-, andthe like)hexyl amine, di(n-, iso-, t-, and the like)cyclohexyl amine,di(n-, iso-, t-, and the like)heptyl amine, di(n-, iso-, t-, and thelike)octyl amine, di(n-, iso-, t-, and the like)decyl amine, di(n-,iso-, t-, and the like)dodecyl amine, di(n-, iso-, t-, and thelike)octadecyl amine, cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine,piperidine, pyrrolidine, and the like; an aliphatic/aromatic amine(e.g., benzyl amine or analogues with longer or additional alkylchains); aromatic amines such as aniline, anisidine, and the like; fusedring amines such as rosin amine, dehydroabietyl amine, dihydroabietylamine, hydroabietyl amine, and the like; and miscellaneous amines (e.g.,adamantyl amine, isonipecotamide, polyoxyalkylenemonoamines, such asM-series Jeffamines available commercially from Huntsman ChemicalCompany of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine, and thelike). It will be obvious to those skilled in the art that small amounts(on a molar basis) of polyamines could also be incorporated into thereaction mixture to produce oligomeric species in the resins if sodesired. The preferred amine is octadecyl amine.

Preferred alcohols to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins of this invention include anymonohydric alcohol. For instance, the monohydric alcohol could be anyaliphatic alcohol e.g., a C₁ -C₂₂ or higher linear alcohol, any branchedalcohol or any cyclic aliphatic alcohol such as methanol, ethanol, (n-and iso-)propanol, (n-, iso-, and t-) butanol, (n-, iso-, t-, and thelike) pentanol, (n-, iso-, t-, and the like) hexanol, (n-, iso-, t-, andthe like) octanol, (n-, iso-, t-, and the like) nonanol, (n- andbranched) decanols, (n- and branched) undecanols, (n- and branched)dodecanols, (n- and branched) hexadecanols, (n- and branched)octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like!; analiphatic/aromatic alcohol (e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates or octyl, nonyl, and dodecylphenol,alkoxyphenol); aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like) and othersuitable alcohols (e.g., N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like), as well as multifunctional alcohols such asethylene glycol, diethylene glycol, triethylene glycol,dimethylolpropionic acid, sucrose, polytetramethylene glycol (MW<˜3000),polypropylene glycol (MW<˜3000), polyester polyols (MW<˜3000),polyethylene glycol (MW<˜3000), pentaerythritol, triethanol amine,glycerin, 1,6-hexanediol, N-methyl-N,N-diethanol amine, trimethylolpropane, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and thelike. The preferred alcohol is octadecanol.

Preferred amines to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins or materials of this inventioninclude any monofunctional amine, with the exception of tertiary aminesvoid of other nucleophilic functional groups (e.g., triethylamine). Forinstance, the monoamine could be any aliphatic primary or secondaryamine e.g., a C₁ -C₂₂ or higher linear amine, any branched amine or anycyclic aliphatic amine such as methyl amine, ethyl amine, (n- andiso-)propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-, t-, andthe like) pentyl amine, (n-, iso-, t-, and the like) hexyl amine, (n-,iso-, t-, and the like) octyl amine, (n-, iso-, t-, and the like) nonylamine, (n- and branched) decyl amine, (n- and branched) undecyl amine,(n- and branched) octadecyl amine, (n- and branched) hexadecyl amine,(n- and branched) dodecyl amine, dimethyl amine, diethyl amine, di(n-,and iso-)propyl amine, di(n-, iso-, t-)butyl amine, di(n-, iso-, t-, andthe like)pentyl amine, di(n-, iso-, t-, and the like)hexyl amine, di(n-,iso-, t-, and the like)cyclohexyl amine, di(n-, iso-, t-, and thelike)heptyl amine, di(n-, iso-, t-, and the like)octyl amine, di(n-,iso-, t-, and the like)decyl amine, di(n-, iso-, t-, and thelike)octadecyl amine, di(n-, iso-, t-, and the like)dodecyl amine,cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine, piperidine,pyrrolidine, and the like!; any aliphatic/aromatic amines (e.g., benzylamine or analogues with longer or additional alkyl chains); aromaticamines such as aniline, anisidine, and the like; fused ring amines suchas rosin amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietylamine, and the like; and miscellaneous amines (e.g., adamantyl amine,isonipecotamide, polyoxyalkylenemono-, di-, or triamines, such as M-,D-, and T-series Jeffamines available commercially from HuntsmanChemical Company of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine,and the like, as well as multifunctional amines such as polyethyleneimine; ethylene diamine; hexamethylene diamine; isomers ofcyclohexyldiamines; 1,3-pentadiamine; 1,12-dodecanediamine;3-dimethylaminopropylamine; 4,7,10-trioxa-1,13-tridecanediamine;diethylene triamine; 3,3-diamino-N-methyldipropylamine;tris(2-aminoethyl)amine, and the like. The preferred amine isoctadecylamine.

Additionally, hydroxyl/amino containing compounds can be employed (withdi- and higher functionality isocyanates taking advantage of thedifference in reactivity of the amine over the hydroxyl group, or withmonoisocyanates reacting with the amine preferentially or with both theamine and the hydroxyl groups). Examples of this include ethanolamine,diethanolamine, and the like.

Additionally amides or other nucleophile containing compounds can bereacted with the isocyanates (mono, di, and the like). Some examplesinclude: urea, oleamide, stearamide, or the like.

Preferred precursors to the isocyanate-derived resins or materials andwaxes of the present invention include mono-, di- and otherpoly-isocyanates. Examples of monoisocyanates includeoctadecylisocyanate; octylisocyanate; butyl and t-butylisocyanate;cyclohexyl isocyanate; adamantyl isocyanate; ethylisocyanatoacetate;ethoxycarbonylisocyanate; phenylisocyanate; alphamethylbenzylisocyanate; 2-phenylcyclopropyl isocyanate; benzylisocyanate;2-ethylphenylisocyanate; benzoylisocyanate; meta andpara-tolylisocyanate; 2-, 3-, or 4-nitrophenylisocyanates;2-ethoxyphenyl isocyanate; 3-methoxyphenyl isocyanate;4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like. Examples of diisocyanatesinclude isophorone diisocyanate (IPDI); toluene diisocyanate (TDI);diphenylmethane-4,4'-diisocyanate (MDI); hydrogenateddiphenylmethane-4,4'-diisocyanate (H,₁₂ MDI); tetra-methyl xylenediisocyanate (TMXDI); hexamethylene- 1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3'-dimethoxy-4,4'-biphenyldiisocyanate;3,3'-dimethyl-4,4'-bimethyl-4,4'-biphenyldiisocyanate; phenylenediisocyanate; 4,4'-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4'-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; and cyclohexylene diisocyanate and its isomers;uretidione dimers of HDI; and the like. Examples of triisocyanates ortheir equivalents include the trimethylolpropane trimer of TDI, and thelike, isocyanurate trimers of TDI, HDI, IPDI, and the like, and biurettrimers of TDI, HDI, IPDI, and the like. Examples of higher isocyanatefunctionalities include copolymers of TDI/HDI, and the like, as well asMDI oligomers.

Phase change inks of this invention contain a phase change carriersystem or composition. The phase change carrier composition is generallydesigned for use in either a direct printing mode or use in an indirector offset printing transfer system. In the direct printing mode, thephase change carrier composition is generally made up of one or morechemicals that provide the necessary properties to allow the phasechange ink (1) to be applied in a thin film of uniform thickness on thefinal receiving substrate when cooled to the ambient temperature afterprinting directly to the substrate; (2) to be ductile while retainingsufficient flexibility so that the applied image on the substrate willnot fracture upon bending; and (3) to possess a high degree oflightness, chroma, transparency and thermal stability. In an offsetprinting transfer or indirect printing mode, the phase change carriercomposition is designed to possess not only the above mentionedproperties, but certain fluidic and mechanical properties necessary foruse in such a system, as described in U.S. Pat. No. 5,389,958 which ishereby incorporated by reference in pertinent part. The phase changeinks of the current invention incorporate isocyanate-derived waxes andisocyanate-derived resins as all or as part of the carrier compositionand can be a supplemental ingredient or supplemental ingredients to theexisting commercial phase change carrier composition. Theisocyanate-derived materials of the current invention are tailored tohave the desirable properties mentioned above when used in the carriercomposition of the inks of the present invention by varying one or moreof the readily available commodity chemical precursors.

The phase change carrier compositions of the current invention may beused in combination with conventional phase change ink colorantmaterials such as Color Index (C.I.) Solvent Dyes, Disperse Dyes,modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes,and/or polymeric dyes such as those disclosed in U.S. patent applicationSer. No. 08/381,610, now U.S. Pat. No. 5,621,022 and/or pigments. Theymay also be used in combination with the isocyanate-derived coloredresins of co-pending U.S. patent application Ser. No. 08/672,617, filedJun. 28, 1996, filed concurrently herewith and assigned to the assigneeof the present invention, to produce a phase change ink.

Prior art phase change inks for use in direct and indirect transferprinting systems are described in U.S. Pat. Nos. 4,889,560 and5,372,852. These inks consist of a phase change ink carrier compositioncomprising one or more fatty amide-containing materials, usuallyconsisting of a mono-amide wax and a tetra-amide resin, one or moretackifiers, one or more plasticizers and one or more antioxidants, incombination with compatible colorants. A preferred tetra-amide resin isa dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and stearic acid. A preferred mono-amide isstearyl stearamide. A preferred tackifier resin is a glycerol ester ofhydrogenated abietic (rosin) acid and a preferred antioxidant is thatprovided by Uniroyal Chemical Company under the tradename Naugard 524.The isocyanate-derived resins and/or isocyanate-derived waxes of thepresent invention replace one or more of the ingredients in the abovephase change ink carrier composition or the inks of the presentinvention can have all of the above ingredients replaced by theisocyanate-derived resins or materials and/or waxes of the presentinvention. The advantages of inks formulated with isocyanate-derivedresins and/or isocyanate-derived waxes over the prior art phase changeinks are:

(1) The isocyanate-derived resins or materials and waxes of thisinvention are very pure, being free of salts and other insolublecontaminants. This makes the inks made from these materials easy tofilter and provides for high reliability in ink jet printing devices.This is a major advantage.

(2) The isocyanate-derived resins or materials and waxes of thisinvention are specifically tailored to give certain physical propertiesthat optimize the performance of the inks of this invention in ink jetprinting devices and on the output substrate. These desirable inkproperties include melting point, viscosity, transparency and thedynamic mechanical properties referenced in the aforementioned U.S. Pat.No. 5,389,958.

(3) The isocyanate-derived resins or materials of this invention can beused in certain combinations with other phase change ink carriermaterials to give ink compositions that display an improved yield stressversus temperature curve over prior art ink compositions. This enablesink droplets to be spread and fused at elevated temperatures during thefusing and transfer steps in an indirect printing process, but at alower pressure than was possible with prior art inks.

Many other patents describe other materials for use in phase change inkjet inks. Some representative examples include U.S. Pat. Nos. 3,653,932;4,390,369; 4,484,948; 4,684,956; 4,851,045; 5,006,170; 5,151,120; EPApplication Nos. 0187352 and 0206286; and PCT Patent Application WO94/04619. These other materials can include paraffins, microcrystallinewaxes, polyethylene waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides and other waxy materials, sulfonamide materials,resinous materials made from different natural sources (tall oil rosinsand rosin esters are an example) and many synthetic resins, oligomers,polymers, co-polymers, and ionomers. It will be obvious to those skilledin the art that the isocyanate-derived materials of this invention couldbe used in inks made from many different combinations of thesematerials.

The aforementioned U.S. Pat. No. 5,496,879 and German patentpublications DE 4205636AL and DE 4205713AL, assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co., describe materials used for phasechange or hot melt gravure printing. It will be obvious to those skilledin the art that the isocyanate-derived materials of this currentinvention would be compatible with those materials and could also beused in that application or other similar printing methods that employhot melt ink technology.

It also will be obvious to those skilled in the art that other inkcolors besides the subtractive primary colors are desirable forapplications, such as postal marking or industrial marking and labelingusing phase change printing, and that this invention is applicable tothese needs. Infrared (IR) or ultraviolet (UV) absorbing dyes can alsobe incorporated into the inks of this invention for use in applicationssuch as "invisible" coding or marking of products.

The inks of the present invention can be equally well employed inapparatus for direct or indirect (offset) printing applications. Whenemployed in direct printing applications a suitable method of printingor producing a layer of a phase change colored ink directly on thesurface of a substrate can comprise:

(1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

(2) transferring the solid phase, phase change colored ink compositionto a phase change ink application means or print head;

(3) raising the operating temperature of the application means or printhead to a level whereby a liquid phase, phase change colored inkcomposition is formed;

(4) providing a substrate in proximity to the application means;

(5) applying a predetermined pattern of the liquid phase, phase changecolored ink composition to at least one surface of the substrate; and

(6) lowering the temperature of the applied ink composition to form asolid phase, phase change ink pattern on the substrate.

An appropriate direct printing process is described in greater detail inU.S. Pat. No. 5,195,430.

When employed in indirect or offset printing applications a suitablemethod of printing or producing a layer of a phase change colored inkindirectly on the surface of a substrate by transferring from anintermediate transfer surface can comprise:

(1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

(2) transferring the solid phase, phase change colored ink compositionto a phase change ink application means or a print head;

(3) raising the operating temperature of the application means or printhead to a level whereby a liquid phase, phase change colored inkcomposition is formed;

(4) providing an intermediate transfer surface in proximity to theapplication means;

(5) applying a predetermined pattern of the liquid phase, phase changecolored ink composition to the intermediate transfer surface;

(6) lowering the temperature of the applied ink composition to form asolid phase, phase change ink pattern on the intermediate transfersurface at a second, intermediate temperature;

(7) transferring said phase change ink composition from the intermediatetransfer surface to a final substrate; and

(8) fixing the phase change ink composition to the substrate to form aprinted substrate, the phase change ink composition having (a) acompressive yield strength which will allow it to be malleable to spreadand deform without an increase in stress when compressive forces areapplied thereto at the second operating temperature, and sufficientinternal cohesive strength to avoid shear banding and weak behavior whensaid phase change ink composition is transferred and fixed to saidsubstrate, and (b) a ductility on the substrate after fixing.

An appropriate offset or indirect printing process is described ingreater detail in U.S. Pat. No. 5,389,958.

The present invention is further described in detail by means of thefollowing Examples and Comparisons. All parts and percentages are byweight and all temperatures are degrees Celsius unless explicitly statedotherwise. It is to be noted that while the following examples mayrecite only one colorant, it is to be understood that each individualexample is only illustrative and any of the primary colorants (cyan,yellow, magenta and black) used in subtractive color printing could beemployed in each instance.

EXAMPLE 1 The Reaction Product of Hydroabietyl Alcohol and IsophoroneDiisocyanate

About 391.9 grams (1.351 moles) of Abitol E hydroabietyl alcohol¹ wasadded to a 1000 ml four-neck resin kettle equipped with a Truborestirrer, an N₂ atmosphere inlet, 200 ml addition funnel, and athermocouple-temperature controller. The kettle was heated to about 100°C. with stirring under an N₂ atmosphere and about 150.0 grams (0.676moles) of isophorone diisocyanate² was added to the addition funnel.About 0.50 grams of dibutyltindilaurate³ catalyst was added to theAbitol E, followed by dropwise addition of the isophorone diisocyanateover 3 hours. The temperature was gradually increased to about 155° C.during this 3 hour period. After an additional 2 hours at about 155° C.,a Fourier Transform Infrared Spectroscopy (FT-IR) of the product was runto insure all of the isocyanate (NCO) was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies were used toconfirm this. The final di-urethane resin product was poured intoaluminum molds and allowed to cool and harden. This final product was aclear solid resin at room temperature characterized by the followingphysical properties: viscosity of about 4,072.9 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 72.0° C. to about 76.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about48° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 2 The Reaction Product of 1.5 Parts Hydroabietyl Alcohol, 0.5Parts Octadecyl Amine, and Isophorone Diisocyanate

About 240.2 grams (0.676 moles) of hydroabietyl alcohol¹ was added to a1000 ml four-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, 200 ml addition funnel, and a thermocouple-temperaturecontroller. About 100.0 grams (0.45 moles) of isophorone diisocyanate²was added to the addition funnel. Agitation of the hydroabietyl alcoholfirst was begun and then all of the isophorone diisocyanate was addedover approximately 5 minutes. About 0.22 grams of dibutyltindilaurate³catalyst was added and the reaction mixture heated to about 125° C.under an N₂ atmosphere. After 4 hours at 125° C., about 59.95 grams(0.225 moles) of octadecyl amine⁴ was added and the temperature raisedto about 150° C. and held for approximately 2 hours. An FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding to ureafrequencies and about 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹corresponding to urethane frequencies were used to confirm this. Thefinal mixed urethane/urea resin product was poured into aluminum moldsand allowed to cool and harden. This final product was a clear solidresin at room temperature characterized by the following physicalproperties: viscosity of about 314.8 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof from about 67.9° C. to about 87.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about23° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 3 The Reaction Product of 1.25 Parts Hydroabietyl Alcohol.0.75Parts Octadecyl Amine and Isophorone Diisocyanate

About 150.1 grams (0.422 moles) of hydroabietyl alcohol¹ and about 75.0grams (0.338 moles) of isophorone diisocyanate² were added to a 500 mlthree-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, and a thermocouple-temperature controller. Agitationwas begun and then about 0.22 grams of dibutyltindilaurate³ catalyst wasadded and the reaction mixture heated to about 130° C. under an N₂atmosphere. After 4 hours at about 130° C., about 67.45 grams (0.253moles) of octadecyl amine⁴ was added and the temperature raised to about150° C. and held for approximately 2 hours. An FT-IR of the reactionproduct was run to insure all of the NCO functionality consumed. Theabsence (disappearance) of a peak at about 2285 cm⁻¹ (NCO) and theappearance (or increase in magnitude) of peaks at about 1705-1635 cm⁻¹and about 1515-1555 cm⁻ corresponding to urea frequencies and about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies were used to confirm this. The final mixed urethane/urearesin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 275.0 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C., a melting point of from about68.4° C. to about 89.0° C. as measured by an electrothermal capillarymelting point apparatus, and a T_(g) of about 17° C. as measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter at ascan rate of 20° C./minute.

EXAMPLE 4 The Reaction Product of 1 Part Hydroabietyl Alcohol, 1 PartOctadecyl Amine and Isophorone Diisocyanate

About 120.1 grams (0.338 moles) of hydroabietyl alcohol¹ and about 75.0grams (0.338 moles) of isophorone diisocyanate² was added to a 500 mlthree-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, and a thermocouple-temperature controller. Agitationwas begun and then about 0.22 grams of dibutyltindilaurate³ catalyst wasadded and the reaction mixture heated to about 90° C. under an N₂atmosphere. After 1 hour at about 90° C. the temperature was increasedto about 110° C. and held for 2 hours. About 89.93 grams (0.338 moles)of octadecyl amine⁴ was added and the temperature raised to about 130°C. and held for approximately 2 hours. An FT-IR of the reaction productwas run to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1705-1635 cm⁻¹ and about1515-1555 cm⁻¹ corresponding to urea frequencies and about 1740-1680cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethane frequencies wereused to confirm this. The final mixed urethane/urea resin product waspoured into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 15.7 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a meltingpoint of from about 73.2° C. to about 110° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about16° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 5 The Reaction Product of Octylphenol Ethoxylate and IsophoroneDiisocyanate

About 450.4 grams (1.802 moles) of Triton X15 octylphenol ethoxylate¹and about 200.0 grams (0.901 moles) of isophorone diisocyanate² wasadded to a 1000 ml three-neck resin kettle equipped with a Truborestirrer, an N₂ atmosphere inlet, and a thermocouple-temperaturecontroller. The mixture was agitated for 10 minutes and then about 0.33grams of dibutyltindilaurate³ catalyst was added and the reactionmixture heated to about 150° C. under an N₂ atmosphere. After 5.5 hoursat about 150° C. an FT-IR of the product was run to insure all of theNCO was consumed. The absence (disappearance) of a peak at about 2285cm⁻¹ (NCO) and the appearance (or increase in magnitude) of peaks atabout 1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies were used to confirm this. The final di-urethane resinproduct was poured into aluminum molds and allowed to cool and harden.This final product was a clear solid resin at room temperaturecharacterized by the following physical properties: viscosity of about124.7 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C., a melting point of from about 51.3° C. to about 81.9° C.as measured by an electrothermal capillary melting point apparatus, anda T_(g) of about 36° C. as measured by differential scanning calorimetryusing a DuPont 2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 6 The Reaction Product of Octadecyl Alcohol, Octadecyl Amine andIsophorone Diisocyanate

About 243.2 grams (0.901 moles) of octadecyl alcohol¹ and about 200.0grams (0.901 moles) of isophorone diisocyanate² were added to a 1000 mlthree-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, and a thermocouple-temperature controller. Agitationwas begun and then about 0.33 grams of dibutyltindilaurate³ catalyst wasadded and the reaction mixture heated to about 90° C. under an N₂atmosphere. After 4 hours the temperature was raised to about 120° C.and about 239.8 grams (0.901 moles) of octadecyl amine⁴ was added over15 minutes. The temperature was raised to about 150° C. and held forapproximately 4 hours. An FT-IR of the product was run to insure all ofthe NCO functionality was consumed. The absence (disappearance) of apeak at about 2285 cm⁻¹ (NCO) and the appearance (or increase inmagnitude) of peaks at about 1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹corresponding to urea frequencies and about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies were used toconfirm this. The final mixed urethane/urea resin product was pouredinto aluminum molds and allowed to cool and harden. This final productwas a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 39.9 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a meltingpoint of from about 63.2° C. to about 92.0° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about-29° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 7 The Reaction Product of Octadecyl Alcohol and IsophoroneDiisocyanate

About 103.14 grams (0.382 moles, 0.382 equiv.) of octadecyl alcohol¹ wasadded to a 500 ml four-neck resin kettle equipped with a Truborestirrer, an N₂ atmosphere inlet, a 200 ml addition funnel, and athermocouple-temperature controller. The kettle was heated to about 80°C. with stirring under an N₂ atmosphere and about 42.4 grams (0.191moles, 0.382 equiv.) of isophorone diisocyanate² was added to theaddition funnel. Isophorone diisocyanate was then added dropwise over 1hour at about 80° C. The temperature was increased to about 120° C. andheld for 3 hours. An FT-IR of the product was run to insure all of theNCO functionality was consumed. The absence (disappearance) of a peak at2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) of peaksat 1740-1680 cm⁻¹ and 1540-1530 cm⁻¹ corresponding to urethanefrequencies were used to confirm this. The final di-urethane resinproduct was poured into aluminum molds and allowed to cool and harden.This final product was a clear solid resin at room temperaturecharacterized by the following physical properties: viscosity of about10.8 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C., and a melting point of about 51.2° C. as measured by anelectrothermal capillary melting point apparatus. An attempt was made tomeasure the T_(g) using differential scanning calorimetry with a DuPont2100 calorimeter at a scan rate of 20° C./minute, but the T_(g) wasdetermined not to be measurable.

EXAMPLE 8 The Reaction Product of Octadecyl Amine and IsophoroneDiisocyanate

About 359.7 grams (1.351 moles) of octadecyl amine¹ was added to a 1000ml four-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, addition funnel (200 ml), and thermocouple-temperaturecontroller. The kettle was heated to about 70° C. with stirring under anN₂ atmosphere and about 150 grams (0.676 moles) of isophoronediisocyanate² was added to the addition funnel. Isophorone diisocyanatewas then added dropwise to the octadecyl amine over 2 hours with thetemperature gradually increased to about 165° C. as the viscosityincreased. The contents were held at about 165° C. for 1 hour and anFT-IR of the product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding to ureafrequencies were used to confirm this. The final di-urea resin productwas poured into aluminum molds and allowed to cool and harden. Thisfinal product was a clear solid resin at room temperature characterizedby the following physical properties: viscosity of about 988.0 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 140° C., amelting point of from about 84.4° C. to about 93.9° C. as measured by anelectrothermal capillary melting point apparatus, and a T_(g) of about-14° C. as measured by differential scanning calorimetry using a DuPont2100 calorimeter at a scan rate of 20° C./minute.

EXAMPLE 9 The Reaction Product of Octadecyl Amine andOctadecylisocyanate

About 250.0 grams (0.877 moles) of octadecylisocyanate¹ and about 233.3grams (0.877 moles) of octadecylamine² were added to a 1000 mlthree-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, and thermocouple-temperature controller. The kettlewas heated to about 130° C. with stirring under an N₂ atmosphere andheld for 6 hours. An FT-IR of the product was run to insure all of theNCO functionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1705-1635 cm⁻¹ and about 1515-1555 cm⁻¹ corresponding tourea frequencies were used to confirm this. The final mono-urea waxproduct was poured into aluminum molds and allowed to cool and harden.This final product was a white waxy solid at room temperaturecharacterized by the following physical properties: viscosity of about13.2 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C., and a melting point of from about 113.4° C. to about113.6° C. as measured by an electrothermal capillary melting pointapparatus.

EXAMPLE 10 The Reaction Product of Octadecyl Alcohol andOctadecylisocyanate

About 250.0 grams (0.877 moles) of octadecylisocyanatel and about 236.7grams (0.867 moles) of octadecyl alcohol² was added to a 1000 mlthree-neck resin kettle equipped with a Trubore stirrer, an N₂atmosphere inlet, and a thermocouple-temperature controller. The kettlewas heated to about 120° C. with stirring under an N₂ atmosphere andabout 0.5 grams of dibutyltindilaurate³ catalyst was added. The reactionmixture was heated at about 120° C. for approximately 4 hours, thenincreased to about 140° C. and held for 2 hours. An FT-IR of the productwas run to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740-1680 cm⁻¹ and about1540-1530 cm⁻¹ corresponding to urethane frequencies were used toconfirm this. The final mono-urethane wax product was poured intoaluminum molds and allowed to cool and harden. This final product was awhite waxy solid at room temperature characterized by the followingphysical properties: viscosity of about 3.7 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., and a meltingpoint of from about 84.5° C. to about 87.7° C. as measured by anelectrothermal capillary melting point apparatus.

EXAMPLE 11 Cyan Ink Made From Mono-Amide Wax, Urethane Resin andTackifier Resin

About 62.5 grams of the di-urethane resin reaction product from Example5, about 62.5 grams of a rosin ester tackifier resin availablecommercially as Arakawa KE-100¹, about 125 grams of stearyl stearamideavailable commercially as Witco S-180² and about 0.4 grams of UniroyalNaugard 445 antioxidant³ were combined in a stainless steel beaker. Thematerials were melted together at a temperature of about 140° C. in anoven, then blended by stirring in a temperature controlled mantle atabout 115° C. for about 1/2 hour. To this mixture was added about 5grams of Solvent Blue 44. After stirring for about 1/2 hour, the cyanink was filtered through a heated Mott apparatus (available from MottMetallurgical) using #3 Whatman filter paper and a pressure of 15 psi.The filtered phase change ink was poured into molds and allowed tosolidify to form ink sticks. This final ink product was characterized bythe following physical properties: viscosity of about 12.4 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 140° C., amelting point of about 90° C. as measured by differential scanningcalorimetry using a DuPont 2100 calorimeter, and a T_(g) of about 42° C.as measured by Dynamic Mechanical Analysis using a Rheometrics SolidsAnalyzer (RSARI). The spectral strength of the ink was determined usinga spectrophotographic procedure based on the measurement of the colorantin solution by dissolving the solid ink in butanol and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the ink was measured as about 2705milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 12 Cyan Ink Made From Amide Wax, Mixed Urethane/Urea Resin andTackifier Resin

In a stainless steel beaker were combined about 62.5 grams of thereaction product mixture of urethane/urea resin material from Example 6,about 65 grams of a rosin ester tackifier resin available commerciallyas Arakawa KE-100¹, about 120 grams of Witco S-180² stearyl stearamideand 0.4 grams of Uniroyal Naugard 445 antioxidant³. The materials weremelted together at a temperature of about 140° C. in an oven, thenblended by stirring in a temperature controlled mantle at about 115° C.for about 1/2 hour. To this mixture was added about 5 grams of SolventBlue 44. After stirring for about 1/2 hour, the cyan ink was filteredthrough a heated Mott apparatus (available from Mott Metallurgical)using #3 Whatman filter paper and a pressure of about 15 psi. Thefiltered phase change ink was poured into molds and allowed to solidifyto form ink sticks. This final ink product was characterized by thefollowing physical properties: viscosity of about 12.9 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a meltingpoint of about 88° C. as measured by differential scanning calorimetryusing a DuPont 2100 calorimeter, and a T_(g) of about 41° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII). The spectral strength of the ink was determined using aspectrophotographic procedure based on the measurement of the colorantin solution by dissolving the solid ink in butanol and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the ink was measured as about 2698milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 13 Cyan Ink Made From Amide Wax, Urethane Resin and TackifierResin

In a stainless steel beaker were combined about 57.5 grams of thediurethane resin reaction product from Example 1, about 57.5 grams of arosin ester tackifier resin available commercially as Arakawa KE-100¹,about 135 grams of Witco S-180 stearyl stearamide² and about 0.5 gramsof Uniroyal Naugard 445 antioxidant³. The materials were melted togetherat a temperature of about 140° C. in an oven, then blended by stirringin a temperature controlled mantle at about 115° C. for about 1/2 hour.To this mixture was added about 5 grams of Solvent Blue 44. Afterstirring for about 1/2 hour, the cyan ink was filtered through a heatedMott apparatus (available from Mott Metallurgical) using #3 Whatmanfilter paper and a pressure of about 15 psi. The filtered phase changeink was poured into molds and allowed to solidify to form ink sticks.This final ink product was characterized by the following physicalproperties: viscosity of about 13.2 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C., a melting pointof about 90° C. as measured by differential scanning calorimetry using aDuPont 2100 calorimeter, and a T_(g) of about 49° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).The spectral strength of the ink was determined using aspectrophotographic procedure based on the measurement of the colorantin solution by dissolving the solid ink in butanol and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the ink was measured as about 2721milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 14 Cyan Ink Made From Amide Wax, Urethane Resin and Urea Resin

About 56.25 grams of the di-urethane resin reaction product from Example5, about 56.25 grams of the di-urea resin reaction product from Example8, about 137.5 grams of Witco S-180 stearyl stearamidel and about 0.5grams of Uniroyal Naugard 445 antioxidant² were combined in a stainlesssteel beaker. The materials were melted together at a temperature ofabout 140° C. in an oven, then blended by stirring in a temperaturecontrolled mantle at about 115° C. for about 1/2 hour. To this mixturewas added about 5 grams of Solvent Blue 44. After stirring for about 1/2hr., the cyan ink was filtered through a heated Mott apparatus(available from Mott Metallurgical) using #3 Whatman filter paper and apressure of about 15 psi. The filtered phase change ink was poured intomolds and allowed to solidify to form ink sticks. This final ink productwas characterized by the following physical properties: viscosity ofabout 14.1 cPs as measured by a Ferranti-Shirley cone-plate viscometerat about 140° C., a melting point of about 90° C. as measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter, and aT_(g) of about 30° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII). The spectral strength of the inkwas determined using a spectrophotographic procedure based on themeasurement of the colorant in solution by dissolving the solid ink inbutanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 2690 milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 15 Cyan Ink Made From Amide Wax. Urethane Resin and MixedUrethane/Urea Resin

About 70 grams of the reaction product urethane material from Example 5,about 70 grams of the reaction product urethane/urea mixture materialfrom Example 6, about 110 grams of Witco S-180 stearyl stearamide¹ andabout 0.5 grams of Uniroyal Naugard 445 antioxidant² were combined in astainless steel beaker. The materials were melted together at atemperature of about 140° C. in an oven, then blended by stirring in atemperature controlled mantle at about 115° C. for about 1/2 hour. Tothis mixture was added about 5 grams of Solvent Blue 44. After stirringfor about 1/2 hour, the cyan ink was filtered through a heated Mottapparatus (available from Mott Metallurgical) using #3 Whatman filterpaper and a pressure of about 15 psi. The filtered phase change ink waspoured into molds and allowed to solidify to form ink sticks. This finalink product was characterized by the following physical properties:viscosity of about 12.9 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., a melting point of about 88° C. as measuredby differential scanning calorimetry using a DuPont 2100 calorimeter,and a T_(g) of about 24° C. as measured by Dynamic Mechanical Analysisusing a Rheometrics Solids Analyzer (RSAII). The spectral strength ofthe ink was determined using a spectrophotographic procedure based onthe measurement of the colorant in solution by dissolving the solid inkin butanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 2714 milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 16 Yellow Ink Made From Urethane Wax, Urethane Resin, TackifierResin and Polymeric Dye

In a stainless steel beaker were combined about 77.8 grams of thereaction product urethane material from Example 5, about 77.7 grams of arosin ester tackifier resin available commercially as Arakawa KE-100¹,about 132.5 grams of the reaction product mono-urethane wax materialfrom Example 10 (stearyl stearurethane) and about 0.5 grams of UniroyalNaugard 445 antioxidant. The materials were melted together at atemperature of about 140° C. in an oven, then blended by stirring in atemperature controlled mantle at about 115° C. for about 1/2 hour. Tothis mixture was added about 11.6 grams of Milliken Chemical Y869polymeric colorant. After stirring for about 1/2 hour, the yellow inkwas filtered through a heated Mott apparatus (available from MottMetallurgical) using #3 Whatman filter paper and a pressure of about 15psi. The filtered phase change ink was poured into molds and allowed tosolidify to form ink sticks. This final ink product was characterized bythe following physical properties: viscosity of about 11.8 cPs asmeasured by a Ferranti-Shirley cone-plate viscometer at about 140° C.and a melting point of about 80° C. as measured by differential scanningcalorimetry using a DuPont 2100 calorimeter. The T_(g) of the final inkproduct was not measured. The spectral strength of the ink wasdetermined using a spectrophotographic procedure based on themeasurement of the colorant in solution by dissolving the solid ink inbutanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 726 milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 17 Black Ink Made From Urethane Wax, Urethane Resin and UreaResin

In a stainless steel beaker were combined about 79.3 grams of thereaction product urethane material from Example 5, about 79.3 grams ofthe reaction product urea resin material from Example 8, about 135 gramsof the reaction product mono-urethane wax material from Example 10(stearyl stearurethane) and about 0.5 grams of Uniroyal Naugard 445antioxidant¹. The materials were melted together at a temperature ofabout 140° C. in an oven, then blended by stirring in a temperaturecontrolled mantle at about 115° C. for about 1/2 hour. To this mixturewas added about 5.8 grams of Solvent Black 45. After stirring for about1/2 hour, the black ink was filtered through a heated Mott apparatus(available from Mott Metallurgical) using #3 Whatman filter paper and apressure of about 15 psi. The filtered phase change ink was poured intomolds and allowed to solidify to form ink sticks. This final ink productwas characterized by the following physical properties: viscosity ofabout 15.2 cPs as measured by a Ferranti-Shirley cone-plate viscometerat about 140° C., a melting point of about 81° C. as measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter, and aT^(g) of about 25° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII). The spectral strength of the inkwas determined using a spectrophotographic procedure based on themeasurement of the colorant in solution by dissolving the solid ink inbutanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 583 milliliters--Absorbance Units per gram at λ_(max).

EXAMPLE 18 Cyan Ink Made From Amide Wax, Mixed Urethane/Urea Resin andCyan Colored Urethane Resin

In a stainless steel beaker were combined about 250 grams of the cyancolored resin from Example 2 of co-pending U.S. patent application Ser.No. 08/672,655 filed Jun. 28, 1996 filed concurrently herewith andassigned to the assignee of the present invention, about 250 grams ofthe reaction product urethane/urea mixture material from Example 2,about 540 grams of Witco S-180 stearyl stearamidel and about 2.0 gramsof Uniroyal Naugard 445 antioxidant². The materials were melted togetherat a temperature of 140° C. in an oven, then blended by stirring in atemperature controlled mantle at about 115° C. for about 1/2 hour. Tothis mixture was added about 5 grams of Solvent Blue 44. After stirringfor about 1/2 hour, the cyan ink was filtered through a heated Mottapparatus (available from Mott Metallurgical) using #3 Whatman filterpaper and a pressure of about 15 psi. The filtered phase change ink waspoured into molds and allowed to solidify to form ink sticks. This finalink product was characterized by the following physical properties:viscosity of about 13.0 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., a melting point of about 89° C. as measuredby differential scanning calorimetry using a DuPont 2100 calorimeter,and a T_(g) of about 27.5° C. as measured by Dynamic Mechanical Analysisusing a Rheometrics Solids Analyzer (RSAII). The spectral strength ofthe ink was determined using a spectrophotographic procedure based onthe measurement of the colorant in solution by dissolving the solid inkin butanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 1069 milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 19 Yellow Ink Made From Amide Wax, Mixed Urethane/Urea Resin andYellow Colored Urethane Resin

In a stainless steel beaker were combined about 98.6 grams of thecolored resin from Example 1 of co-pending U.S. patent application Ser.No. ₋₋₋₋₋₋, Docket No. USA 6169 filed concurrently herewith and assignedto the assignee of the present invention, about 80.7 grams of thematerial from Example 2, about 179 grams of Witco S-180 stearylstearamide¹ and about 0.7 grams of Uniroyal Naugard 445 antioxidant².The materials were melted together at a temperature of about 140° C. inan oven, then blended by stirring in a temperature controlled mantle atabout 115° C. for about 1/2 hour. The yellow ink was then filteredthrough a heated Mott apparatus (available from Mott Metallurgical)using #3 Whatman filter paper and a pressure of about 15 psi. Thefiltered phase change ink was poured into molds and allowed to solidifyto form ink sticks. This final ink product was characterized by thefollowing physical properties: viscosity of about 13.6 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a meltingpoint of about 90° C. as measured by differential scanning calorimetryusing a DuPont 2100 calorimeter, and a T_(g) of about 20° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII). The spectral strength of the ink was determined using aspectrophotographic procedure based on the measurement of the colorantin solution by dissolving the solid ink in butanol and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the ink was measured as about 1497milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 20 Black Ink Made From Amide Wax, Mixed Urethane/Urea Resin andBlack Colored Urethane Resin

In a stainless steel beaker were combined about 301 grams of the coloredresin from Example 3 of co-pending U.S. patent application Ser. No.₋₋₋₋₋₋, Docket No. USA 6169 filed concurrently herewith and assigned tothe assignee of the present invention, about 374 grams of the reactionproduct urethane/urea mixture material from Example 2, about 802 gramsof Witco S-180 stearyl stearamidel and about 3.0 grams of UniroyalNaugard 445 antioxidant². The materials were melted together at atemperature of about 140° C. in an oven, then blended by stirring in atemperature controlled mantle at about 1 15° C. for about 1/2 hour. Theblack ink was then filtered through a heated Mott apparatus (availablefrom Mott Metallurgical) using #3 Whatman filter paper and a pressure ofabout 15 psi. The filtered phase change ink was poured into molds andallowed to solidify to form ink sticks. This final ink product wascharacterized by the following physical properties: viscosity of about13.3 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C., a melting point of about 89° C. as measured bydifferential scanning calorimetry using a DuPont 2100 calorimeter, and aT_(g) of about 16° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII). The spectral strength of the inkwas determined using a spectrophotographic procedure based on themeasurement of the colorant in solution by dissolving the solid ink inbutanol and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the ink was measuredas about 869 milliliters·Absorbance Units per gram at λ_(max).

EXAMPLE 21 Yield Stress versus Temperature Curve for the Ink FromExample 20 Compared to a Prior Art Phase Change Ink

FIG. 1 is a graphical representation of the compression yield data forthe ink of Example 20 plotted versus a prior art phase change ink foundin Example 2 of U.S. Pat. No. 5,372,852. The tests were done on a MTSSYNTECH 2/D mechanical tester using cylindrical sample blocks of amount19 millimeters by 19 millimeters in size.

These results show that the test ink from Example 20 requires lesspressure to fuse the test ink at elevated temperatures than the priorart ink and is therefore better adapted for offset printingapplications, although it is also suitable for direct printing.

PRINT TESTING

The inks in examples 11-20 were tested in a Tektronix Phaser® 340printer, which uses an offset transfer printing system. All of the aboveinks were found to completely transfer and to give images of good color,print quality and durability either as primary colors or when used incombination with each other or the commercially available Phaser® 340printer inks.

The inks in Examples 18-20 were tested in a Tektronix Phaser® 300printer, which uses a direct printing system. All of the above inks werefound to give images of good color, print quality and durability eitheras primary colors or when used in combination with each other or thecommercially available Phaser® 300 printer inks.

PHYSICAL PROPERTIES OF SELECTED WAXES, RESINS, AND INKS

Tables 1 and 2 are used to illustrate the differences in physicalproperties that can be achieved by the proper selection of functionalityin analogous test molecules.

                  TABLE 1                                                         ______________________________________                                        Analogous Waxes                                                                            MELTING POINT                                                                              VISCOSITY @ 140° C.                          ______________________________________                                        Stearyl Stearurethane                                                                      84° C.                                                                              3.7 cPs                                             (EXAMPLE 10)                                                                  Stearyl Stearamide                                                                         92° C.                                                                              5.9 cPs                                             (Witco S-180)                                                                 Stearyl Stearurea                                                                          113° C.                                                                             13.2 cPs                                            (EXAMPLE 9)                                                                   ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Analogous Stearyl/IPDI Products                                                            MELTING POINT                                                                              VISCOSITY @ 140° C.                          ______________________________________                                        Stearyl/IPDI Urethane                                                                      48° C.                                                                              11 cPs                                              (EXAMPLE 7)                                                                   Mixed Stearyl/IPDI                                                                         82° C.                                                                              40 cPs                                              Urea/Urethane                                                                 (EXAMPLE 6)                                                                   Stearyl/IPDI Urea                                                                          107° C.                                                                             988 cPs                                             (EXAMPLE 8)                                                                   ______________________________________                                    

Table 3 illustrates the difference in physical properties of resins thatcan be obtained by mixing both functionality and molecular shape andsize.

                  TABLE 3                                                         ______________________________________                                        Mixtures of Abietic Alcohol and Stearyl Amine, Reacted                        with IPDI                                                                     Alcohol/Amine Ratio                                                                           T.sub.g 's/Melting Point/Viscosity                            ______________________________________                                        100% Alcohol    48° C./72-76° C./4079 cPs @140° C.       (EXAMPLE 1)                                                                   75% Alcoho1/25% Amine                                                                         23° C./68-87° C./315 cPs @140° C.        (EXAMPLE 2)                                                                   62.5% Alcohol/37.5% Amine                                                                     17° C./68-89° C./275 cPs @140° C.        (EXAMPLE 3)                                                                   50% Alcohol/50% Amine                                                                         16° C./73-110° C./15.7 cPs @140° C.      (EXAMPLE 4)                                                                   ______________________________________                                    

While the invention has been described above with reference to specificembodiments thereof, it is apparent that many changes, modifications andvariations can be made without departing from the inventive conceptdisclosed herein. For example, it should be noted where a urethanereaction product is obtained, a single alcohol precursor or multiplealcohol precursors may be used with an appropriate isocyanate as long asthe required stoichiometric ratio is maintained. Similarly, where a ureais the reaction product, a single amine precursor or multiple amineprecursors may employed as long as the required stoichiometric ratio ismaintained. Where a urethane/urea reaction product is obtained, singleor multiple alcohol and amine precursors may be employed within theappropriate stoichiometric ratios. Accordingly, it is intended toembrace all such changes, modifications and variations that fall withinthe spirit and broad scope of the appended claims. All patentapplications, patents and other publications cited herein areincorporated by reference in their entirety.

What is claimed is:
 1. A phase change ink carrier composition comprisingin combination;(a) a urethane/urea isocyanate-derived material; (b) atackifier, and (c) a mono-amide.
 2. The phase change ink carriercomposition of claim 1 further comprising an anti-oxidant.
 3. The phasechange ink carrier composition of claim 1 wherein the urethane/ureaisocyanate-derived material is the reaction product of the reaction ofthe following reactants:(a) at least one alcohol; (b) an isocyanate, and(c) at least one monoamine.
 4. The phase change ink carrier compositionof claim 3 wherein the alcohol is selected from the group of monohydricalcohols consisting of an aliphatic alcohol, an aromatic alcohol, analiphatic/aromatic alcohol, a fused ring alcohol, and mixtures thereof.5. The phase change ink carrier composition of claim 4 wherein thealcohol is selected from the group consisting of hydroabietyl alcohol,octylphenol ethoxylate and octadecyl alcohol.
 6. The phase change inkcarrier composition of claim 3 wherein the isocyanate is selected fromthe group consisting of a monoisocyanate, a diisocyanate, atriisocyanate, a copolymer of a diisocyanate, and a copolymer of atriisocyanate.
 7. The phase change ink carrier composition of claim 6wherein the isocyanate is isophorone diisocyanate.
 8. The phase changeink carrier composition of claim 3 wherein the amine is selected fromthe group of monoamines consisting of an aliphatic monoamine, anaromatic monoamine, an aliphatic/aromatic monoamine, a fused ring systemmonoamine, and a hydroxyl/monoamino containing compound.
 9. The phasechange ink carrier composition of claim 8 wherein the monoamine isoctadecyl amine.
 10. The phase change ink carrier composition of claim 3further comprising mixing and heating the alcohol, the monoamine and theisocyanate in an inert atmosphere.
 11. The phase change ink carriercomposition of claim 10 further comprising using nitrogen as the inertatmosphere.
 12. The phase change ink carrier composition of claim 3further comprising a colorant to thereby form an ink composition. 13.The phase change ink carrier composition of claim 12 wherein thecolorant is a dye, a colored resin or a pigment.
 14. The phase changeink carrier composition of claim 1 wherein the tackifier is a rosinester.
 15. The phase change ink carrier composition of claim 14 whereinthe rosin ester a glycerol rosin ester.
 16. A method for producing alayer of a phase change ink on a surface of a substrate, whichcomprises:(1) forming a phase change ink composition in the solid phasecomprising an admixture of (a) a phase change carrier composition and(b) a compatible colorant material; the phase change carrier compositionbeing a reaction product comprising a urethane/urea mixture formed bythe reaction of at least one alcohol reactant with at least oneisocyanate reactant and at least one amine reactant; (2) transferringthe solid phase, phase change ink composition to a phase change inkapplication means; (3) raising the operating temperature of theapplication means to a level whereby a liquid phase, phase change inkcomposition is formed; (4) providing a substrate in proximity to theapplication means; (5) applying a predetermined pattern of the liquidphase, phase change ink composition to at least one surface of thesubstrate; (6) lowering the temperature of the applied ink compositionto form a solid phase, phase change ink pattern on the substrate.
 17. Amethod for producing a layer of a phase change ink on a surface of asubstrate, which comprises:(1) employing in a printing apparatus a phasechange ink composition in the solid phase comprising an admixture of (a)a phase change carrier composition and (b) a compatible colorantmaterial; the phase change carrier composition being a reaction productcomprising a urethane/urea mixture formed by the reaction of at leastone alcohol reactant with at least one isocyanate reactant and at leastone amine reactant; (2) applying the phase change ink composition in adesired pattern to an intermediate transfer surface; (3) transferringthe desired pattern of the phase change ink composition to the surfaceof the substrate.